CN1615327A - Method of treating polyester polymer and polyester polymer reduced in low-boiling component content - Google Patents
Method of treating polyester polymer and polyester polymer reduced in low-boiling component content Download PDFInfo
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- CN1615327A CN1615327A CNA038020688A CN03802068A CN1615327A CN 1615327 A CN1615327 A CN 1615327A CN A038020688 A CNA038020688 A CN A038020688A CN 03802068 A CN03802068 A CN 03802068A CN 1615327 A CN1615327 A CN 1615327A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/287—Raw material pre-treatment while feeding
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/88—Post-polymerisation treatment
- C08G63/90—Purification; Drying
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
A method for polyester polymer treatment which comprises heating a polyester polymer C obtained by subjecting at least one cyclic ester compound B comprising [epsilon]-caprolactone to ring-opening polymerization with a polymer A having a hydroxy group and/or ester bond, at a temperature which is 115 DEG C or higher and below 170 DEG C and is lower than the melting point of the polyester polymer C, while keeping the polymer C in a solid state to thereby remove organic low-boiling components v from the polymer C obtained by the polymerization. Thus, a polyester polymer from which [epsilon]-caprolactone and caprolactone dimers have been sufficiently removed can be obtained without causing deterioration or alteration of resin properties, deterioration of hue, or decrease of profitability.
Description
Technical field
The present invention relates to a kind of for polymkeric substance with hydroxyl and/or ester bond and the polyester polymer that contains the cyclic ester class ring-opening polymerization gained of 6-caprolactone, under solid states such as powder body, the gas of heating is circulated therein, with the treatment process of removing organic low boiling point component (being designated hereinafter simply as low boiling point component), the polyester polymer that reaches the remarkable minimizing of low boiling point component containing ratio.
Background technology
For example make the segmented copolymer of 6-caprolactone and crystalline aromatic polyester ring-opening polymerization gained as polyester polymer, owing to have caoutchouc elasticity and high heat resistance, so be widely used as various molded articles, film, silk, reach the expanding material of polyester usefulness shock-resistance modifying agent, polyester alloy.
Yet above-mentioned segmented copolymer owing to contain low boiling point component such as unreacted 6-caprolactone, produces so have the problem of monomer stink etc. generally when reaction is finished.
Therefore, inquired into from above-mentioned segmented copolymer and removed low boiling point component.Yet, owing to be about 60 ℃ low value as the polycaprolactone fusing point of epsilon caprolactone homopolymer, so when residual monomer is purpose above-mentioned segmented copolymer is handled to remove with solid state usually.In fact for example carry out dewatered processing under 40 ℃ in low-down temperature, even but long time treatment, still can't fully remove monomer.
In flat 3-263425 number each communique opened in Japanese Patent Publication 52-49037 number, special fair 8-9661 number, special fair 7-76263 number, spy, introduced remaining monomer methods in the polyester type block copolymer of removing the ring-opening polymerization gained by crystalline aromatic polyester and lactone, be under reduced pressure, carry out the method for demonomerization under the temperature more than the fusing point as this method.These methods are all carried out reduced pressure treatment under fusion, though the resin of gained lowers monomeric stink, do not contain high density monomer etc. but still change.Moreover, because at high temperature when handling, the influence of being heated is big, causes resin rerum natura or form and aspect to worsen.
In addition, in opening clear 60-31525 number, special fair 5-23290 number each communique, the spy put down in writing, polyester type block copolymer that will be by crystalline aromatic polyester and lactone ring-opening polymerization gained is further at fusing point or below the fusing point, carry out polymerization with solid state shape under 170～215 ℃, more the method for making of high molecular weight polymers.These methods are heat treated under vacuum or under the gas communication all, but when carrying out polycondensation efficiently, not only must be at fusing point or below the fusing point but also must under very high temperature, handle, and must handle for a long time.This processing is under solid state and can produce problems such as painted, resin deterioration.Therefore, when under gas communication, carrying out solid state polymerization, must use very highly purified nitrogen gas, have no alternative but make the very disadvantageous economically condition enactment that comprises treatment temp, treatment time.And, when under solid state shape, carrying out polycondensation energetically,, then cause the uneven situation of the inner generation of resin because the degree of carrying out polycondensation at solid surface and further portion produces difference, for example molecular weight, molecular weight distribution, acid number etc. change.In addition, owing to can't make solid shape, temperature, gas communication etc., so keep constant in being difficult for making every batch or by the reaction between criticizing in itself for fully uniformly.
In addition, make polyester polymer under the condition that high density moisture exists during heating and melting, because the deterioration of the resin rerum natura that produces because of hydrolysis takes place, so carry out usually to remove the drying operation that moisture is purpose.And this drying operation is selected more economical condition with hydrolysis usually in the scope that big influence can not arranged resin shaping, is to be equal to or less than under the condition of 100ppm to carry out at moisture concentration generally speaking.Under this condition, can't fully remove remaining monomer or particularly as the high-melting-point composition of 6-caprolactone dipolymer (being designated hereinafter simply as the caprolactone dipolymer) etc.
Summary of the invention
Therefore, the problem that desire of the present invention solves is 6-caprolactone and the caprolactone dipolymer that makes in the polyester polymer, fully removes under the situation that can not produce the deterioration of resin rerum natura deterioration or variation and form and aspect, economy reduction.
The inventor etc. are for from by the remaining 6-caprolactone of attenuating the polymkeric substance with hydroxyl and/or ester bond and the polyester polymer (C) of cyclic ester class ring-opening polymerization gained that contains 6-caprolactone and the treatment process of caprolactone dipolymer, found that of further investigation, polymkeric substance (C) is under solid state, make and be heated to the melting temperature that is lower than polymkeric substance (C) and gas (g) circulation in specific low temperature range, but then remove organic low boiling point component of following in the autohemagglutination compound (C) (v), can solve this problem thus, so finished the present invention.
In other words, the 1st treatment process that provides a kind of polyester polymer of the present invention, it is characterized in that, to have the polymkeric substance of hydroxyl and/or ester bond and the polyester polymer (C) that (B) contains the cyclic ester class ring-opening polymerization gained of 6-caprolactone by (A), solid state, be heated to 115 ℃～be lower than 170 ℃ and be lower than the fusing point of polyester polymer (C), from polymkeric substance (C), remove low boiling point component (v) whereby by the polymerization gained.
The 2nd treatment process that provides the polyester polymer of record among the 1st of the present invention of the present invention, wherein make the heating of polyester polymer (C) solid state, be by make be heated to 115 ℃～carry out down less than 170 ℃ and gas (g) circulation that is lower than the melting temperature of polyester polymer (C).
The 3rd treatment process that provides the polyester polymer of record in the of the present invention the 1st or the 2nd of the present invention, wherein solid state is powder shaped, granular or sheet.
The 4th treatment process that provides the polyester polymer of each record in the 1st～3 of the present invention of the present invention, wherein the Heating temperature of polyester polymer (C) under solid state is 120～150 ℃.
The 5th treatment process that provides the polyester polymer of each record in the 1st～4 of the present invention of the present invention, wherein gas (g) contains the oxygen of 1～22vol%.
The 6th treatment process that provides the polyester polymer of each record in the 1st～5 of the present invention of the present invention, wherein polymkeric substance (A) is a crystalline aromatic polyester.
The 7th treatment process that provides the polyester polymer of each record in the 1st～6 of the present invention of the present invention, wherein the fusing point of polyester (A) is more than 150 ℃ or 150 ℃.
The 8th treatment process that provides the polyester polymer of each record in the 1st～7 of the present invention of the present invention, (gas v) is reused in processing wherein to remove low boiling point component the gas (g ') after the circulation that produces from making gas (g) circulation.
The 9th treatment process that provides the polyester polymer of each record in the 1st～8 of the present invention of the present invention, wherein organic low boiling point component (v) contains 6-caprolactone and/or 6-caprolactone dipolymer.
The 10th of the present invention provides a kind of polyester polymer, this polymkeric substance is that the 6-caprolactone in the polymkeric substance (C) and the concentration of caprolactone dipolymer are all and are equal to or less than 450ppm by polymkeric substance with hydroxyl and/or ester bond (A) and the polyester polymer (C) that contains cyclic ester class (B) the ring-opening polymerization gained of ε-lactone.
The 11st of the present invention provides polyester polymer of the present invention the 10th, and wherein the concentration of 6-caprolactone and caprolactone dipolymer is all and is equal to or less than 100ppm.
Graphic simple declaration
Fig. 1 is the schema that the embodiment example of treatment process of the present invention is shown.
Fig. 2 is the schema that another embodiment example of treatment process of the present invention is shown.
Nomenclature
1 mixing tank
The supply opening of 2 polymkeric substance (A)
The supply opening of 3 monomers (B)
4 reactors
5 cooling layers
6 tablets presss
7 hoppers
7 ' resin supply opening
8 treatment unit
9 gas supply openings
10 gas discharge outlets
11 materials-stored box
11 ' resin relief outlet
12 low boiling point component tripping devices
13 resin relief outlets
14 agglutinative low boiling point component relief outlets
The outlet of 15 regeneration gass
The preferred plan that carries out an invention
The following describes embodiment of the present invention.
Polyester polymer of the present invention (C) is to make by polymkeric substance (A) with hydroxyl and/or ester bond and cyclic ester class (B) (also being called monomer (the B)) ring-opening polymerization that contains 6-caprolactone.Below, each polymerization composition of relevant polyester polymer (C) is described.
The cyclic ester class (B) that contains 6-caprolactone
The cyclic ester class (B) that contains 6-caprolactone of the present invention refers to 6-caprolactone mixture independent or 6-caprolactone and the cyclic ester class except that 6-caprolactone.In other words, 6-caprolactone is must composition.
Can enumerate intermolecular cyclic ester, 6-caprolactone or other lactone of hydroxycarboxylic acid as above-mentioned cyclic ester class (B).
Lactone is meant to have intramolecularly cyclic ester constructor.Therefore, as lactone, particularly, 6-caprolactone or other lactone as necessary composition in the lactone, can enumerate, α, alpha-alpha-dimethyl-beta-propiolactone, dodecane lactone, beta-propiolactone, butyrolactone, penta propyl ester, 3-alkyl penta propyl ester, β, β-dialkyl group penta propyl ester, hydroxyl hexahydrobenzoic acid derive and the lactone that comes, Isocoumarin 〉97, tonka bean camphor, Hydroxycoumarin, 2-benzo [c] furanone etc.
These materials that comprise 6-caprolactone separately ring-opening polymerization making polyester polymer, can also with the intermolecular cyclic ester class copolymerization of hydroxycarboxylic acid more than a kind.At this moment, the ratio of intermolecular cyclic ester and lactone can be looked purpose polymers and be carried out various variations, but by selecting the combination of various intermolecular cyclic esters and lactone, can add is mutually preferable character.Crystallinity for the cyclic ester class after reduction, the adjustment polymerization is effective especially.
And the present invention also can use and the similar lactams of cyclic ester class (B), can also use the mixture of cyclic ester class (B) and caprolactam class.Lactams is meant to have intramolecularly cyclic amide constructor.Particularly can enumerate ε-Ji Neixianan, δ-Valerolactim, butyrolactam, azetidinone etc.Among these, to use ε-Ji Neixianan, butyrolactam etc. preferable.
The intermolecular cyclic ester of hydroxycarboxylic acid is the product of the hydroxycarboxylic acid of identical or different kind of quasi-molecule in the esterification of intermolecular dehydration ring-type.Representational material is for example by shown in the following general formula (1).
(wherein, R
1, R
2, R
3, R
4Can be identical or different mutually, each represents hydrogen atom, methyl or ethyl)
As hydroxycarboxylic acid, can enumerate, lactic acid, oxyacetic acid, ethyl hexanol acid and dimethyl ethanol acid, Alpha-hydroxy valeric acid, Alpha-hydroxy isovaleric acid, Alpha-hydroxy caproic acid, Alpha-hydroxy isocaproic acid, HMV, Alpha-hydroxy enanthic acid, Alpha-hydroxy are sad, Alpha-hydroxy capric acid, Alpha-hydroxy tetradecanoic acid, Alpha-hydroxy stearic acid etc.
As two molecule cyclic esters with a kind of hydroxycarboxylic acid, can enumerate, for example diglycolide (promptly 1,4-two oxa-s-hexanaphthene-2, the 5-diketone, also abbreviate glycollide as), dilactide (promptly 1,4-two oxa-s-3,6-dimethyl cyclohexane-2, the 5-diketone, also abbreviate rac-Lactide as), two (ethyl glycollide), two (dimethyl glycollide), or L-lactic acid or D-lactic acid, for example in the L-of each intermolecular ring-type esterification dilactide, the D-dilactide, D, the D of two molecule ring-type esterifications of L-lactic acid, the L-dilactide, the dilactide class of the MESO-dilactide of each a part ring-type esterification of L-lactic acid or D-lactic acid etc.
As the cyclic ester of different hydroxycarboxylic acids, can enumerate for example methyl glycollide, α, alpha-alpha-dimethyl glycollide, trimethylammonium glycollide etc.
Intermolecular cyclic ester used in the present invention is that the characteristic of looking purpose polymers is selected, and can 2 kinds or multiple being used in combination.When for example using dilactide, not only use L-dilactide or D-dilactide separately as dilactide as the multipolymer of dilactide and diglycolide, and be to be selected from L-dilactide, D-dilactide, D, in L-dilactide, the MESO-dilactide 2 kinds or multiple dilactide and diglycolide make up, and realize better resin properties with regard to the resin crystallinity at aspects such as plasticity or the transparency, thermotolerances.
The cyclic ester class of using simultaneously with 6-caprolactone preferably has identical with 6-caprolactone or more lower boiling in essence cyclic ester class in the present invention.
Polymkeric substance (A) with hydroxyl and/or ester bond
Polymkeric substance (A) with hydroxyl and/or ester bond used in the present invention refers to polymkeric substance with hydroxyl, has the polymkeric substance of ester bond or have hydroxyl and the polymkeric substance of ester bond.
As polymkeric substance with hydroxyl, can enumerate, for example polyvinyl alcohol, starch, Mierocrystalline cellulose, ether of cellulose, making near grafting when using these easily is the polymeric polymkeric substance, makes the polymkeric substance near block polymerization as polyoxy alkylidene ether easily.
In addition, as having ester bond and not having a polymkeric substance of hydroxyl, can enumerate, for example polyvinyl acetate (PVA), vinyl acetate/ethylene copolymer, polyacrylic ester, polyacrylic ester based copolymer, polycarbonate etc.
As having ester bond but do not have hydroxyl and endways on have the polymkeric substance of carboxyl, can enumerate, for example polyesteramide, aliphatic polyester, present cycloaliphatic polyesters, crystalline aromatic polyester, crystalline aromatic are the polyester elastomer of principal constituent etc.
When there is not hydroxyl in end, because speed of response is very slow, so preferably add the micro-moisture that is used for the hydrolyzable moiety ester or as the additive (alcohol etc.) (this additive can use following molecular weight adjustment agent) of promotor.
As polymkeric substance, can enumerate partial esterification cellulose ester, polyesteramide, aliphatic polyester, present cycloaliphatic polyesters, crystalline aromatic polyester etc. with hydroxyl and ester bond.
These can 2 kinds or multiple mixing use.
Wherein better with crystalline aromatic polyester.
Crystalline aromatic polyester mainly is meant by being selected from terephthalic acid, m-phthalic acid, terephthalic acid, 2, at least a aromatic dicarboxylic acids such as 6-naphthalene dicarboxylic acids, and/or 4-hydroxy-benzoic acid or 6-hydroxyl-2-naphthoic acid, with be selected from ethylene glycol, propylene glycol, 1, ammediol, 1, the 4-butyleneglycol, pentanediol, hexylene glycol, ethohexadiol, neopentyl glycol, cyclohexanedimethanol, the hydrogenation dihydroxyphenyl propane, Xylene glycol, Diethylene Glycol, triethylene glycol, dipropylene glycol, dibutylene glycol, at least a kind of aliphatic diol in the polyalkylene glycols such as polytetramethylene glycol constitutes.Also can comprise 4-amido phenylformic acid etc. as minor constituent.
Crystalline aromatic polyester is preferable more than 180 ℃ or 180 ℃ with fusing point.Can enumerate polyethylene terephthalate, polybutylene terephthalate, PEN, PBN and be the polyester elastomer that the center constitutes particularly with these.
And, be no more than in the scope of 10 moles of % as the molar ratio of dicarboxylic acid composition in whole dicarboxylic acid compositions, also can use the aliphatic dicarboxylic acid that is selected from succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, undecane dicarboxylic acid, cyclohexane dicarboxylic acid, dimeracid.
The crystalline aromatic polyester terminal group has hydroxyl in essence with use or the carboxyl person is preferable.
Can use above-mentioned polymkeric substance or these mixtures more than 2 kinds or 2 kinds as polymkeric substance of the present invention (A), there is no particular limitation, but preferable to have abundant intensity person as the shaping thing.
Polymkeric substance (A) is to be molecular weight the greater, and particularly its weight-average molecular weight (Mw) is that 5,000～300,000 weight-average molecular weight preferable, better person is 10,000～200,000.The melt viscosity that particularly adds mixing condition because melt viscosity more difficult with mixing of cyclic ester class and resulting polymers (C) also uprises, can be brought into play effect of the present invention, so be preferred during greater than the high viscosity of 2,000 pools more significantly.
Polyester polymer (C)
Polyester polymer (C) for example mixes under the heating and melting state with the polymkeric substance with hydroxyl and/or ester bond (A), stirs and make by the cyclic ester class (B) that will contain above-mentioned 6-caprolactone fat.
Look the character of its purpose polymers (C) and different in when reaction polymkeric substance (A) and the additional proportion of monomer (B), but part by weight (B)/(A) is generally 99/1～1/99, the preferably is 5/95～75/25, better person is 10/90～60/40.
The temperature of reaction of ring-opening polymerization is looked its employed raw material and is different, but is 150～190 ℃ with 125～200 ℃ of preferable, better persons when cyclic ester class (B) contains 2 molecule cyclic esters.When cyclic ester only is made of lactone, it is 180～250 ℃ with 150～300 ℃ of preferable, better persons.In addition, temperature of reaction is preferable with the temperature than the temperature of low 15 ℃ of the fusing point of polymkeric substance (A) or softening temperature～high 50 ℃, and better person is the softening temperature or the fusing point～high 20 ℃ temperature of polymkeric substance (A).It is 150～260 ℃ particularly with 125～300 ℃ of preferable, better persons.When particularly using crystalline aromatic polyester, it is 225～260 ℃ with 180～300 ℃ of preferable, better persons.
Monomer (B) is under the rare gas element or reactor is full of under the state of polymerization composition, promptly do not have in essence under the state of gas phase part and carries out for the ring-opening polymerization of polymkeric substance (A).Pressure when the preferably reacts is under normal pressure or add to depress and carry out.
The reactivity of monomer (B), particularly 6-caprolactone can be set arbitrarily, when the reactivity of monomer (B) is high the polymerization velocity of cyclic ester class reduce outer, when carrying out the reaction of transesterify etc., when particularly using crystalline aromatic polyester as polymkeric substance (A), the fusing point of polymkeric substance (C) reduces.The preferable reactivity of monomer (B) is that 75～99 moles of %, preferably are 90～97.5 moles of %.
Concentration as 6-caprolactone remaining in the reaction reaction system (being crude polymer (C)) at the end is that 0.3～10 weight %, preferably are 1～5 weight %, and the concentration of caprolactone dipolymer is that 0.05～1 weight %, preferably are 0.1～0.5 weight %.
The reactivity of the raw material type of visual use of reaction times and ratio thereof, temperature of reaction, target and changing, being generally 0.2～10 hour, preferably and being 0.5～5 hour, better person is 0.5～2 hour.
Intrasystem maximum reaction pressure is 2～200kg/cm
2, the preferably is 2～50kg/cm
2, better person is 2～20kg/cm
2
This ring-opening polymerization also can catalyst-free, but generally also can carry out in the presence of the adoptable catalyzer in ring-opening polymerization, esterification, transesterification reaction.Preferred catalyzer is metal, these organometallic compound, organic acid salt, alcohol or phenates, halogenide etc. such as lithium, sodium, potassium, caesium, magnesium, calcium, barium, strontium, zinc, aluminium, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, cadmium, manganese.Better person is organotin, organoaluminum, organic titanic compound, organotin-carboxylate, organotin halogenide, tin carboxylate salt, tin halide, triisobutyl aluminium, tri-alkoxy aluminium, tetrabutyl titanate, germanium dioxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.These catalyzer can more than 2 kinds or 2 kinds and be used.
And, it is required that this polyreaction is looked its purpose, can make water, lactic acid, oxyacetic acid and other alcohol or carboxylic acid equimolecular quantity conditioning agent (chain-transfer agent), have the functional group's of the carboxyl, hydroxyl and other ester forming bases that are selected from more than 3 or 3 as the functional group compound, then can obtain low-molecular-weight polymkeric substance.In addition, general employed antioxidant as other polymeric additives, UV light absorber, softening agent etc. can be used with being not particularly limited, and these can make an addition in the reaction system in the reaction.
In addition, between reaction, except that above-mentioned polymerizable composition, also can append isocyanates, acid anhydrides, have the compound of epoxy group(ing) etc., then can make the polymer properties modification.
Monomer (B) can use the reactor of intermittent type, semibatch or continous way to carry out for the ring-opening polymerization of polymkeric substance (A).Elapsed time changed the reactivity of monomer (B) when intermittent type took out owing to resin, and then, the remaining quantity of contained monomer (B) is changing in the polymkeric substance (C), so reaction is carried out preferable with continous way.And the resin by successive polymerization reaction gained is by stabilizations such as heat-up time, Heating temperatures, and the form and aspect in then can making every batch, molecular weight, fusing point etc. are stable.
As above the polymkeric substance of gained (C) (refer to crude polymer and then abbreviate polymkeric substance (C) as not producing any mixing) is to contain unreacted 6-caprolactone and caprolactone dipolymer.By ring-opening polymerization, be difficult for 6-caprolactone is reduced to non-existent in essence scope.Usually, because the concentration of the remaining 6-caprolactone of ring-opening polymerization speed and reaction system is proportional, so extremely slow in the minimizing speed of reacting final 6-caprolactone.6-caprolactone might depolymerize owing to the polycaprolactone end after the polymerization to react and regenerate, and this point also is considered to be difficult for making 6-caprolactone concentration to be reduced to the ultimate reason.Also thinking simultaneously may be because same reaction generates the caprolactone dipolymer.Because the caprolactone dipolymer also is lower molecular weight, the problem on surface etc. can appear oozing out into when melt-processed, so and 6-caprolactone similarly be the material that should remove.
Polyester polymer (C) depends on the weight-average molecular weight of polymkeric substance (A) and the composition of polymkeric substance (A) and monomer (B), and weight-average molecular weight is that 5,000～500,000 preferable, better person is 10,000～300,000.
Resulting polymers (C) contains low boiling point component, so the present invention makes the gas (g) of heating circulate therein under solid state for polymkeric substance (C), to remove low boiling point component (v).Therefore, polymkeric substance (C) is powder shaped, granular, sheet, strip etc., and the preferably is powder shaped, granular (below be also referred to as " powder body ").The size of powder body (diameter conversion) is that 0.01～10mm, preferably are 0.1～5mm.Be difficult for removing low boiling point component during powder body big or small excessive (v), though and can remove low boiling point component easily (v), if this powder body is difficult for making or handling when too small if the hour meter area increases.
The fusing point of polymkeric substance (C) is more than 170 ℃ or 170 ℃ with preferable more than 150 ℃ or 150 ℃, better person.When fusing point was lower than this value, the problem of existence was, and is softening in the processing, and because own wt, powder body shaped polymer (C) can cause situations such as adhesion.And this treatment process is owing to handle with solid state, need not be heated to that fusing point or fusing point are above, fusing point is high also has no relations.Fusing point carries out demonomerization when handling greater than 200 ℃ polymkeric substance under fusion, then produce the necessity of at high temperature carrying out.Therefore, dystectic polymkeric substance can be brought into play the effect of the inventive method more.
The employed gas of the inventive method (g) is rare gas elementes such as oxygen containing gas such as oxygen, air or nitrogen, helium, argon gas.The treatment temp height, because the influence of oxygen makes characteristic degradation, when problem such as painted takes place, to use rare gas element preferable, owing to need not promote polycondensation among the present invention, available lesser temps is handled, therefore can use the gas air for example that contains aerobic, so economy excellence comparatively.
In addition, when using oxygen containing gas, improve the form and aspect of the polymkeric substance (C) after handling.Therefore, be that the gas (g) of 1～22vol% serves as preferred to use oxygen concn among the present invention.Above-mentioned oxygen concn can be considered low boiling point component (amount v), and be set in and do not have safety to go up the scope of problem.
Gas (g) also can contain moisture, but preferred operation by compression, cooling, absorption etc. before use dehumidifies.
The temperature of gas used in the present invention (g) is 115～less than 170 ℃, preferably be below 165 ℃ or 165 ℃, better person is 120～150 ℃.When the temperature of gas (g) is low than said temperature, make low boiling point component (v), particularly the concentration of caprolactone dipolymer is difficult for fully reducing, when high,, be difficult for keeping rerum natura stable because the rerum natura of polymkeric substance (C) changes in handling than this temperature.
Treatment temp of the present invention is compared with the polymerization temperature of general solid state polymerization, owing to be low-down temperature, the polymkeric substance (C) after then handling does not need the refrigerative engineering, or can implement at short notice.
The flow of gas among the present invention (g) can be changed to optimal value according to the shape or the circulation device of polymkeric substance (C), but can be 100～10,000 times/time of volumetric capacity of the polymkeric substance (C) of solid state.Gas flow after a little while lower boiling (v) the evaporation rate of composition reduces, and it is unfavorable in the time of too much economy to be produced.
The present invention handles employed device, as long as the gas (g) of actual heating is contacted with solid state polymkeric substance (C), has device to all functions that can even processing in addition for preferred.Device can be reactor type, the person that has the agitating wing, can also be device this as vibration, rotation, blunger.In addition, for cylindrical grade or turriform also can, this device is fit to be used in continous way and handles.As long as even in addition can for the turriform device do not need the device of positive stirring powder plastochondria but can make circulated gases evenly circulation function, also can be multilayer disc formula drying machine in addition.Device uses insulation material etc., and the temperature of polymkeric substance (C) is advisable with abundant enhancer in institute's fixed temperature scope, sleeve pipe etc. can also be set in addition, adopt steam, heating agent etc. to be heated to the temperature identical with gas temperature, can also be in obtaining effective scope of the present invention the temperature high or low than gas temperature.In addition, the device pressure inside can be pressurization, normal pressure, decompression, but with normal pressure or reduce pressure preferable.
Treatment process required time of the present invention has no particular limits, to be set between 2～10 hours to good.The actual treatment time looks gaseous species or oxygen concn, gas temperature, gas flow etc. and changes, but considers the target value of low boiling point component concentration in the goods polymkeric substance (C), scope that the resin rerum natura does not have actual change and the improving target value of form and aspect usually and set.
In the present invention, use for making the gas recovery of handling behind the polymkeric substance (C), must be from removing low boiling point component (engineering v) by the operation of cooling, aggegation, absorption etc. from gas discharge outlet expellant gas (g ').In addition, the operation that according to circumstances temporarily keeps the agglutinative low boiling point component and remove.
Among the present invention, gas (g) is good with without interruption, discharge.Heating, the Supply Method of gas (g) have no particular limits.For example use condenser, gas blower etc., or the pressure when utilizing gas storage or pressure is risen, will be supplied to treatment unit by heat exchanger heats to the gas of institute's fixed temperature by heating.
In addition, solid state polymkeric substance (C) can intermittent type, continous way or intermittent type handle.Intermittent type can produce the treatment time distribution when handling, when the concentration of low boiling point component fully reduces, look treatment time difference of the present invention the resin rerum natura is changed, and is no problem on the quality of goods.
Secondly, use drawing explanation the present invention.Fig. 1 illustrates the schema of one embodiment of this invention example.
At first, treatment unit 8 have resin supply opening 7 ', resin relief outlet 11 ', gas supply opening 9, gas discharge outlet 10.Herein, resin is the solid state crude polymer (C) of powder body etc.Resin supply opening and resin relief outlet view apparatus and decide, for example carrying out intermittent type can be for same when handling.And, be supplied to organic low boiling point component tripping device 12 from gas discharge outlet expellant gas (g '), remove low boiling point component by methods such as cooling, aggegation, absorption and (reclaimed v).(v) discharge with self coagulation low boiling point component relief outlet 14 in bulk or continuously with tripping device 12 isolating low boiling point components by device 12.Make the cohesion low boiling point component when discharging in bulk by device 12.And when carrying out processing of the present invention continuously, with the device 12 of use arranged side by side more than 2 or 2, follow handle with the regeneration of discharging with in mutual switch use preferable.Cut apart by powder body shaped polymer (C) or continuously, supply, be expelled to device 8.Gas (g) is being supplied, is being discharged from gas discharge outlet 10 from gas supply opening 9 under the heated condition in advance.
In addition, use Fig. 2 explanation to comprise ring-opening polymerization and carry out embodiment example when of the present invention continuously.The polymkeric substance (A) and the normal temperature of heating and melting state or solid state are descended or pre-heated monomer (B), from each supply opening 2,3 without interruption giving in the mixing tank 1 that can heat, mix, stir.Make the raw material of mixing, preheating without interruption, and carry out polyreaction to the purpose reactivity, give pelletization via cooling tank 5, tablets press 6 to reactor 4.The gained pellet is stored in hopper 7 or does not store and just is supplied to treatment unit 8.Be heated to that the gas of specified temperature is without interruption to be given treatment unit 8 and discharged.Discharge again in materials-stored box 11 thereafter from handling device 8 discharge pellets.
Can stablize the resin rerum natura that keeps purpose polymers (C) by this processing, make the 6-caprolactone and the caprolactone dipolymer amount that comprise in the polymkeric substance be reduced to non-existent in fact amount with the method for less expensive.In other words, the concentration of the 6-caprolactone in the polymkeric substance (C) after handling by the present invention, caprolactone dipolymer is all 450ppm or 450ppm is following, also be all 100ppm or below the 100ppm.Can make the excellent in stability (being that the resin rerum natura does not have in fact to change) of form and aspect, resin rerum natura, the polyester polymer that the low boiling point component containing ratio is low according to the present invention.
The said above-mentioned resin rerum natura of the present invention does not change in fact, refer to molecular weight (or reduced viscosity relevant), molecular weight distribution value the ratio Mw/Mn of number-average molecular weight (Mn) (weight-average molecular weight (Mw) with), acid number, and the reduction degree of fusing point of factors of influence such as being subjected to flowability, physical strength, all can remain in the specialized range by treatment process of the present invention with molecular weight.Particularly, the relevant polymkeric substance (C) of handling front and back according to the present invention, the ratio (value/processing after the processing before value) that is reduced viscosity is 5% to be in 5% with ratio (value before value/processings after the processing) interior, Mw/Mn, and the ratio of acid number (value before value/processings after the processing) is that the 5% reduction degree with interior, fusing point (value after the preceding value-processing of processing) is below 3 ℃ or 3 ℃.
And, acid number is owing to causing that thermolysis, hydrolysis etc. increase, and reduces again when carrying out polycondensation, so be used as the index of resin rerum natura stability, owing at high temperature carry out transesterification reaction and can reduce fusing point, also be used as the index of resin rerum natura stability so fusing point descends.
The said form and aspect excellent in stability of polymkeric substance among the present invention (C), refer to heat treated before compare, the form and aspect assessed value YI after the heat treated, L, a, b are approximately identical value or close value.
[embodiment]
Below, specifically describe the present invention by embodiment, but the present invention is not limited by these.
And, when % and part have no particular limits, all represent weight % and weight part.
(1) fusing point
Adopt differential scanning calorimetric measurement device (DSC), be benchmark, obtain fusing point from fusion peak temperature (Tpm) with JIS K7121; Finish the difference of temperature (Tem) from fusion beginning temperature (Tim) and fusion and obtain the fusing point dispersiveness.
(2) 6-caprolactone concentration, caprolactone bipolymer concentration
Use the system gas chromatograph GC-14A of Shimadzu Seisakusho Ltd., use internal diameter 3.2mm, length 2.1m wherein to fill the glass pillar of 10%PEG20M (liquid phase)/excellent Buddhist nun's Christian Breton HPS (carrier).Correctly measure 0.5g sample and 0.1g phenyl ether, be melted among the 20gHFIP (hexafluoroisopropanol) as the internal standard material.After keeping 8 minutes under 180 ℃ of steady temperatures, be warming up to 220 ℃ inchmeal, arrive stable again maintenance the under 220 ℃ the state.The result who measures gained as carrier with nitrogen adopts the internal standard method to calculate, and asks for 6-caprolactone concentration and caprolactone bipolymer concentration as weight %.
(3) molecular weight distribution
Carry out GPC and measure, convert by standard P MMA and ask for number-average molecular weight and weight-average molecular weight, try to achieve molecular weight distribution (Mw/Mn) from their ratio.The tubing string that GPC measures is to use clear and electrician limited-liability company makes Shodex GPC HFIP-800P, HFIP-805P, HFIP-804P, HFIP-803P, detector is to use the system RID-6A of Shimadzu Seisakusho Ltd., elutriant is to use HFIP, carries out under 50 ℃ of tubing string temperature, flow velocity 1.0ml/min.
(4) reduced viscosity
Measure under the following conditions.
Solvent: phenol/tetrachloroethane (weight ratio)=6/4
Test portion concentration: 50mg/25ml
Measure temperature: 30 ℃
(5) acid number
Take by weighing the 1.0g test portion, in the 50g phenylcarbinol, heat fusion down in 160 ℃.After the water-cooled, add the 50g chloroform and mix, as indicator, carry out titration with 1/10 equivalent KOH ethanolic soln with phenolphthalein.In 10～30 minutes, get suitable 3 as dissolution time, obtain acid number (mgKOH/g) from the value and the difference of the acid value (blank value) of the phenylcarbinol of measuring in addition and each 50g mixed solution of chloroform that are extrapolated to dissolution time 0 timesharing as sample.
(6) form and aspect
Use Japanese electric look industry system colour-difference meter ∑-90 to measure.
The assessed value of form and aspect
YI: expression yellow chromaticity (yellow index).The numerical value of yellow chromaticity is littler, and form and aspect are more excellent.
L: expression gloss, numerical value are bigger, and expression gloss increases to brightness (bleaching) direction more, and numerical value is littler, and expression increases to darkness (blackening) direction more.
A: the colourity of expression form and aspect and chroma, represent that red direction is stronger on the occasion of healing when big, negative value heals and represents that green direction is more by force when big.
B: the colourity of expression form and aspect and chroma, strong on the occasion of the yellow direction that heals when big, negative value heals when big blue direction more by force.
[Production Example 1]
Make 60 parts of fused have the poly terephthalic acid of C-terminal-1,4-butanediol ester (poly-plastic cement corporate system society system (Port リ プ ラ ス チ ッ Network society system)), 40 parts of 6-caprolactones add in the reaction vessel, after nitrogen purge, under 230 ℃, reacted while stirring 1.5 hours, and made thick polyester polymer.Stopping under the whipped state,, taking out thick polyester polymer, be cut into partical after the cooling with strip with nitrogen pressure, via the valve that is arranged at reaction container bottom.The thick polyester polymer of gained, fusing point are that 205.1 ℃, reduced viscosity are 1.350, acid number is 3.13, molecular weight distribution value is 2.05, form and aspect Y1 is 29.4, L is 84.2, a is 4.5, b is 15.2.And comprising 6-caprolactone in thick polyester polymer is that 1.430wt%, caprolactone dipolymer are 1550ppm.The bulk specific gravity of pellet is 0.80, median size (conversion diameter) is 2.9mm.And, do not observe low melting point peak fully by DSC from the polycaprolactone homopolymer.
[Production Example 2]
Continuously ring-opening polymerization equipment is 2 forcing machines by 30mm φ, the L/D=42 of charging feedstock polymkeric substance (A) usefulness, the 6-caprolactone supply that is connected in its venting port with pipe arrangement, the Shi Lusa that is connected in the forcing machine mouth as Shi Lusa (the ス Le ザ-) corporate system of the L/D=9 of static mixer mix device SMX, at the static mixer outlet mouth mould set via toothed gear pump and the tablets press that is cut into partical after bar by the extrusion of mouth mould is cooled off become.
Make the heating of above-mentioned forcing machine remain on 250 ℃, make the poly terephthalic acid-1 identical with Production Example 1, the 4-butanediol ester with 12kg/Hr from the supply of resin input port, under nitrogen, 240 ℃ the temperature of mouthful mould (static mixer with) heating and melting down.Venting port in the forcing machine way is supplied 6-caprolactone with 8kg/Hr, mixes in forcing machine and stirs.The thick polyester polymer of gained, 209.3 ℃ of fusing points, reduced viscosity 1.405, acid number 2.97, molecular weight distribution value 1.95, form and aspect YI are 23.4, L is 88.2, a is 2.7, b is 8.9.And the 6-caprolactone that comprises in the thick polyester polymer is that 1.820wt%, caprolactone dipolymer are 1350ppm.The bulk specific gravity of pellet is 0.80, median size (conversion diameter) is 2.9mm.And, do not observe low melting point peak fully by DSC from the polycaprolactone homopolymer.
[embodiment 1]
Have the thermal medium sleeve pipe, be provided with horizontal stir shaft, from the gas of end supply heating, in the other end is discharged the device of gas, once add the pellet of 15kg, make the air that is heated to 120 ℃ (adopting dehydrating unit to be equivalent to open-air dry in advance for-40 ℃) under normal pressure, with 2.0m from the gas supply opening by the thick polyester polymer of Production Example 2 gained
3/ hour speed (this moment resin temperature almost equate) without interruption with gas temperature, simultaneously the gas that contains low boiling point component is discharged continuously from gas discharge outlet.By remaining in 10 ℃ condenser, other is discharged make low boiling point component aggegation, separation in being filled with the adsorption tower of molecular sieve after through expellant gas.And, be provided with bucket in condenser, temporarily store the agglutinative low boiling point component, discharge via valve from the bucket bottom.After adopting the processing of above-mentioned heated air to carry out 10 hours, cooled off and taken out resin granular material.The analytical value of gained polyester polymer is as shown in table 1.The 6-caprolactone concentration of the polyester polymer in the processing and caprolactone bipolymer concentration are taken a sample in each is fixed time to determine the variation with the elapsed time, use Ka Er Fischer moisture concentration meter (in vapourizing unit, 200 ℃ handle down measured in 20 minutes) to ask for moisture concentration simultaneously, also can confirm the variation in its elapsed time.
In table 1, monomer concentration is an expression 6-caprolactone concentration, and bipolymer concentration is an expression caprolactone bipolymer concentration, and ND is below the expression limit of detection, is at least 50ppm or below the 50ppm.The result is as shown in table 2.
[embodiment 2]
Except that air is changed into the nitrogen, inquire in the same manner with embodiment 1.The analytical value of gained polyester polymer is as shown in table 1.
[embodiment 3]
In the tower moisture eliminator of the dry type of volume 100L bucket type with 80m
3/ hour the air (being equivalent to open-air by dehydrating unit is-40 ℃ of dryings in advance) that is heated to 130 ℃ without interruption under normal pressure is discharged gas continuously from gas discharge outlet simultaneously., discharge via the adsorption tower that is filled with molecular sieve again by remaining in 10 ℃ condenser through expellant gas., at room temperature be fed in this tower moisture eliminator continuously with the pellet of Production Example 2 gained from the device top, the residence time is 6 hours, makes simultaneously continuously with the pellet self-chambering side's of depositing discharge.Afterwards the analytical value of the polyester polymer of gained is as shown in table 1 to handle very stable (in other words, the supply of pellet almost is the steady state that equates with discharge constant, gas temperature with resin temperature).
[comparative example 1]
After carrying out ring-opening polymerization in the same manner with Production Example 1,230 ℃, make the vacuum pump action that connects via cold-trap under stirring, and the decompression degree in the reaction vessel is improved, decompression degree arrival 0.5torr after about 30 minutes.Under this state, keep decompression 1 hour in addition, remove low boiling point component.After stirring stops, with nitrogen pressure, take out with strip, be cut into partical after the cooling via the valve that is arranged at reaction container bottom.The analytical value of gained polyester polymer is as shown in table 1.
[comparative example 2]
Except that the Heating temperature that makes air changes 110 ℃, treatment time into is 12 hours, handles in the same manner with embodiment 1.
[comparative example 3]
To remain in 230 ℃ by screw portion 2 forcing machines that constitute, 30mm φ, L/D=28 that have 4 venting ports and carry out pellet fused kneading portion in fact and remove low boiling point component, and at room temperature the pellet of Production Example 2 gained be supplied with 5kg/Hr from the resin supply opening.After confirming that resin spues,, make to keep decompression in 2 forcing machines, remove low boiling point component by be connected in the vacuum pump of each venting port via cryo trapping.The decompression degree is stable at 0.5torr, makes the resin cooling of taking out with strip after about 1 hour, is cut into partical.The analytical value of the polyester polymer of gained is as shown in table 1.
[comparative example 4]
To remain in 230 ℃ by screw portion 2 forcing machines that constitute, 30mm φ, L/D=42 that have 6 venting ports and carry out pellet fused kneading portion in fact and remove low boiling point component, and at room temperature the pellet of Production Example 2 gained be supplied with 5kg/Hr from the resin supply opening.After confirming that resin spues, reduce pressure by each venting port in the same manner, remove low boiling point component with comparative example.The decompression degree is stable at 0.5torr, makes the resin cooling of taking out with strip after about 1 hour, is cut into partical.The analytical value of the polyester polymer of gained is as shown in table 1.
[comparative example 5]
Except that using high-purity nitrogen, heated air temperature is to shorten to 4 hours in 180 ℃ and treatment time, handles in the same manner with embodiment 1.The analytical value of gained polyester polymer is as shown in table 1.
[comparative example 6]
Though use the device identical with embodiment 1, the gas supply opening airtight and from gas discharge outlet via condenser, adsorption tower connection vacuum pump.Remaining in vacuum tightness under the state of 0.5torr makes bushing temperature be adjusted to 180 ℃, handle 10 hours.The analytical value of the polyester polymer of cooling back, taking-up is as shown in table 1.
[comparative example 7]
Except that treatment temp is 120 ℃, handle in the same manner with comparative example 6.The analytical value of the polyester polymer of gained is as shown in table 1.
According to the present invention the rerum natura of polyester polymer is not had detrimentally affect, and can reduce the concentration of low boiling point components such as 6-caprolactone in the polyester polymer, caprolactone dipolymer.For example use the block copolymerization polymkeric substance of 6-caprolactone and crystalline aromatic polyester, owing to have caoutchouc elasticity and high heat resistance, so can be widely used as various molded articles, film, silk, and the shock-resistance of polyester etc. improve the increase-volume material of material, polyester alloy, owing to do not have monomer stink or low boiling point component to move to resin surface, so also can be used in medical use, food product pack purposes.
Table 1
| Fusing point (℃) | Reduction ratio viscosity | Acid value (mgKOH/ g) | Mw/M ???n | Form and aspect | Monomer concentration (wt %) | Bipolymer concentration (ppm) | ||||
| YI | ?L | ??a | ??b | |||||||
| Embodiment 1 | ?205.1 | ?1.350 | ????3.23 | ??2.05 | 29.4 | ?84.2 | ??4.5 | ??15.2 | ?1.430 | ????1550 |
| Production Example 2 | ?209.3 | ?1.405 | ????2.97 | ??1.95 | 23.4 | ?88.2 | ??2.7 | ??8.9 | ?1.820 | ????1350 |
| Embodiment 1 | ?209.1 | ?1.401 | ????3.00 | ??1.99 | 20.5 | ?92.2 | ??2.0 | ??8.8 | ?ND | ????ND |
| Embodiment 2 | ?209.2 | ?1.406 | ????2.97 | ??2.00 | 23.0 | ?89.1 | ??2.7 | ??9.0 | ?ND | ????ND |
| Embodiment 3 | ?209.4 | ?1.410 | ????2.97 | ??1.94 | 19.9 | ?92.2 | ??1.9 | ??9.0 | ?ND | ????90 |
| Comparative example 1 | ?201.4 | ?1.290 | ????3.55 | ??2.06 | 36.5 | ?79.0 | ??5.7 | ??18.2 | ?0.090 | ????990 |
| Comparative example 2 | ?209.2 | ?1.405 | ????3.00 | ??1.96 | 21.4 | ?91.0 | ??2.2 | ??9.0 | ?ND | ????470 |
| Comparative example 3 | ?207.4 | ?1.395 | ????3.03 | ??2.10 | 25.3 | ?85.3 | ??3.3 | ??9.3 | ?0.078 | ????1030 |
| Comparative example 4 | ?206.9 | ?1.340 | ????3.20 | ??2.22 | 28.4 | ?84.0 | ??4.0 | ??9.6 | ?0.064 | ????930 |
| Comparative example 5 | ?207.7 | ?1.450 | ????2.85 | ??2.30 | 27.2 | ?86.0 | ??3.3 | ??10.5 | ?0.020 | ????250 |
| Comparative example 6 | ?205.2 | ?1.500 | ????2.75 | ??2.44 | 28.3 | ?86.0 | ??3.5 | ??11.0 | ?0.046 | ????890 |
| Comparative example 7 | ?209.3 | ?1.400 | ????2.94 | ??1.97 | 24.0 | ?87.8 | ??2.0 | ??9.1 | ?0.055 | ????990 |
Table 2
| Contain composition | Unit | Embodiment 1 (treatment time, Hr) | |||||||
| ?0 | ????1 | ????2 | ????3 | ????4 | ????6 | ????8 | ?10 | ||
| 6-caprolactone | wt％ | ?1.820 | ????0.480 | ????0.320 | ????0.164 | ????0.095 | ????0.020 | ????0.009 | ?ND |
| The lactone dipolymer | ppm | ?1350 | ????1180 | ????940 | ????718 | ????640 | ????200 | ????60 | ?ND |
| Moisture | ppm | ?1800 | ????450 | ????95 | ????30 | ????10 | ????12 | ????20 | ?10 |
Industrial applicibility
The present invention is both economical method, provide a kind of resin characteristics of doing one's utmost to control by the polyester polymer of the ring-opening polymerisation gained of the polymer with hydroxyl and/or ester bond and 6-caprolactone to change, and can prevent that form and aspect from worsening and required improvement the according to circumstances, and make unreacted monomer and lactone bipolymer concentration be down to algorithmic method of limit.
Claims (11)
1. the treatment process of a polyester polymer, it is characterized in that, make by (A) and have the polymkeric substance of hydroxyl and/or ester bond and the polyester polymer (C) that (B) contains the cyclic ester class ring-opening polymerization gained of 6-caprolactone, under solid state, be heated to 115 ℃～be lower than 170 ℃ and be lower than the fusing point of polyester polymer (C), from the polymkeric substance (C) that adopts the polymerization gained, remove low boiling point component (v).
2. according to the treatment process of the described polyester polymer of claim 1, the wherein heating under the solid state of polyester polymer (C), be by make be heated to 115 ℃～be lower than 170 ℃ and be lower than under gas (g) circulation of melting temperature of polyester polymer (C) and carry out.
3. according to the treatment process of the polyester polymer described in claim 1 or 2, wherein solid state is powder shaped, granular or sheet.
4. according to the treatment process of each described polyester polymer in the claim 1～3, wherein the Heating temperature under the solid state of polyester polymer (C) is 120～150 ℃.
5. according to the treatment process of each described polyester polymer in the claim 1～4, it is characterized in that gas (g) contains the oxygen of 1～22vol%.
6. according to the treatment process of each described polyester polymer in the claim 1～5, wherein polymkeric substance (A) is a crystalline aromatic polyester.
7. according to the treatment process of each described polyester polymer in the claim 1～6, wherein the fusing point of polymkeric substance (A) is more than 150 ℃ or 150 ℃.
8. according to the treatment process of each described polyester polymer in the claim 1～7, wherein (gas v) is used in processing again removing low boiling point component the gas (g ') after the circulation that produces from making gas (g) circulation.
9. according to the treatment process of each described polyester polymer in the claim 1～8, wherein low boiling point component (v) contains 6-caprolactone and/or 6-caprolactone dipolymer.
10. polyester polymer, this polymkeric substance is by polymkeric substance with hydroxyl and/or ester bond (A) and the polyester polymer (C) that comprises cyclic ester class (B) the ring-opening polymerization gained of ε-lactone, it is characterized in that the 6-caprolactone in the polymkeric substance (C) and the concentration of caprolactone dipolymer is all 450ppm or below the 450ppm.
11. according to the polyester polymerization described in the claim 10, wherein the concentration of 6-caprolactone and 6-caprolactone dipolymer is all 100ppm or below the 100ppm.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2002005390A JP3590385B2 (en) | 2002-01-11 | 2002-01-11 | Polyester-based polymer processing method and polyester-based polymer with low content of low boiling components |
| JP5390/2002 | 2002-01-11 |
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| CN1615327A true CN1615327A (en) | 2005-05-11 |
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| US (1) | US20050075464A1 (en) |
| EP (1) | EP1473316A4 (en) |
| JP (1) | JP3590385B2 (en) |
| KR (1) | KR20040079927A (en) |
| CN (1) | CN1615327A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558522A (en) * | 2010-12-28 | 2012-07-11 | 上海杰事杰新材料(集团)股份有限公司 | Method for ring-opening polymerization preparation of degradable polyester from reclaimed polyesters |
| CN105121504A (en) * | 2013-04-19 | 2015-12-02 | 株式会社武藏野化学研究所 | Method for purifying aliphatic polyester and aliphatic polyester purified with said method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1972980B (en) * | 2004-06-25 | 2010-04-07 | 上越农业未来株式会社 | Thermoplastic cellulosic composition, process for producing the same, and molded article thereof |
| US8486135B2 (en) | 2006-06-01 | 2013-07-16 | Abbott Cardiovascular Systems Inc. | Implantable medical devices fabricated from branched polymers |
| US8841412B2 (en) * | 2011-08-11 | 2014-09-23 | Abbott Cardiovascular Systems Inc. | Controlling moisture in and plasticization of bioresorbable polymer for melt processing |
| JP6292827B2 (en) * | 2013-11-07 | 2018-03-14 | 日本合成化学工業株式会社 | Modified ethylene-vinyl ester copolymer saponified resin composition and method for producing the same |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6031525A (en) * | 1983-07-29 | 1985-02-18 | Toyobo Co Ltd | Production of high-viscosity polyester block copolymer |
| US4680345A (en) * | 1985-06-05 | 1987-07-14 | Toyo Boseki Kabushiki Kaisha | Continuous production of elastic polyesters |
| JPS61287922A (en) * | 1985-06-14 | 1986-12-18 | Toyobo Co Ltd | Production of elastic polyester |
| CA2033095C (en) * | 1989-05-17 | 1997-01-14 | Hiromitsu Ishii | Process for continuous production of elastic polyesters |
| TW203079B (en) * | 1991-03-27 | 1993-04-01 | Japan Synthetic Rubber Co Ltd | |
| IT1245600B (en) * | 1991-03-29 | 1994-09-29 | M & G Ricerche Spa | BLOCK COPOLYESTER RESINS |
| US5314927A (en) * | 1992-05-13 | 1994-05-24 | Showa Highpolymer Co., Ltd. | Polyester foamed articles and method for producing the same |
| DE4429524C2 (en) * | 1994-08-19 | 1997-12-18 | Inventa Ag | Process for the preparation of linear copolyesters containing omega-hydroxycarboxylic acid units |
| JP2000085054A (en) * | 1998-09-14 | 2000-03-28 | Daicel Chem Ind Ltd | Collapsible laminate and manufacture thereof |
| TW585880B (en) * | 1999-08-05 | 2004-05-01 | Daicel Chem | Process for producing polyester block copolymer |
-
2002
- 2002-01-11 JP JP2002005390A patent/JP3590385B2/en not_active Expired - Fee Related
-
2003
- 2003-01-08 CN CNA038020688A patent/CN1615327A/en active Pending
- 2003-01-08 WO PCT/JP2003/000085 patent/WO2003059986A1/en not_active Application Discontinuation
- 2003-01-08 EP EP03700497A patent/EP1473316A4/en not_active Withdrawn
- 2003-01-08 KR KR10-2004-7010767A patent/KR20040079927A/en not_active Application Discontinuation
- 2003-01-08 US US10/500,275 patent/US20050075464A1/en not_active Abandoned
- 2003-01-09 TW TW092100372A patent/TW200302237A/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558522A (en) * | 2010-12-28 | 2012-07-11 | 上海杰事杰新材料(集团)股份有限公司 | Method for ring-opening polymerization preparation of degradable polyester from reclaimed polyesters |
| CN105121504A (en) * | 2013-04-19 | 2015-12-02 | 株式会社武藏野化学研究所 | Method for purifying aliphatic polyester and aliphatic polyester purified with said method |
| US9688809B2 (en) | 2013-04-19 | 2017-06-27 | Musashino Chemical Laboratory, Ltd. | Method for purifying aliphatic polyester and aliphatic polyester purified with said method |
| CN105121504B (en) * | 2013-04-19 | 2018-05-01 | 株式会社武藏野化学研究所 | The process for purification of aliphatic polyester and the aliphatic polyester refined with this method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003059986A1 (en) | 2003-07-24 |
| US20050075464A1 (en) | 2005-04-07 |
| JP3590385B2 (en) | 2004-11-17 |
| TW200302237A (en) | 2003-08-01 |
| JP2003206348A (en) | 2003-07-22 |
| EP1473316A1 (en) | 2004-11-03 |
| EP1473316A4 (en) | 2005-09-07 |
| KR20040079927A (en) | 2004-09-16 |
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